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Patented Mar. 18, 1952 UNITED STATES PRINTING F WOQLEN TEXTILES WITH ANQNAQUEOUS PASTE COREPRISENG A DYE- STUFF CQNTAENING AN ACID GROUP, AWATER-IN SOLUBLE VINYL POLYMER, AND AN AID-LIBERATING AGENT Erwin Meier,Neuewelt, near Basel, Switzerland, assignor to Cilia Limited, Basel,Switzerland, a

No Drawing. Application dune 20, 1949, Serial NoJlOlifiQt. inSwitzerland July 2, 1948 9 Claims. 1 The present invention relates'tothe printing of textiles.

In the normal printing of textiles, the usual procedure is to print thematerial to be printed Witha printing paste which contains, in aqueoussuspension or solution, a dyestufi which possesses is capable of verywide application, but is bound up with the disadvantage that theprinting operation requires various manipulations such as printing,drying, steaming, washing, repeated drying, etc., all of'which have tobe carried .out in more or less close succession.

Printing processes have also beenjrecornmended wherein the dyestufiis'fixed on the fiber with the aidoi' a'binding agent.

In this type of process, the 'dyestufi which is employed need not "havean affinity for the textile fiber, so that it "is possible to usepigments and the like as the coloring material. However, it is verydifiicult, in such processes, to realize a sufiicient adherence of thecoloring matter to the fiber, without the incidence of a frequentlyundesirable stiffening of the printed places by means of the bindingagent, so that, notwithstanding the simplicity of the printing proceduretherein, this typeof process .hasnotlfound generalacceptance. It is alsoto .be noted that, :in

many processes of this character, it is necessary to effect a hardeningof the binding agent at temperatures which are considerably higher than:the usual drying temperatures and that, secondly, special heatingchambers are required in order to successfully carry out such processes.

It has now been found that textile structures which are made, whollyorin part, of animal fibers 01' other fibers havingsimilar dyeingproperties, can be advantageously printed With dyeistufis -.which haveaffinity for these fibers, if use :isqmade of a printing paste which, inaddition to the .dyestufi, contains a non-aqueous thickener whichcomprises a water-insoluble polymer as well as anagent-which splits oiiacid.

As textiles structures of the said type, use may be made moreparticularly of fabrics and knitted articles made. of animal fibers orfibers whic have a similar dyeing behavior, for example fab- 2 rics madeof superpolyamides, or of silk, or particularly of wool. In connectionwith the use of wool, it is important that, in practicing the presentinvention, use may be made of chlorinated wool and also of unchlorinatedwool.

The dyestuffs to be used according to the present invention must possessaffinity for the'fibers which are employed. As such, the so-called basicdyestuiis, for example, can be used. However, use may be made withadvantage of dyestuffs with acid groups, for example acid dyestuifssuchas are conventionally used for dyeing .wool. .Suc'h acid dyestuiis maybe monoazo anddisazo .dye-

stuffs which contain acid groups, such as carboxylic acid or sulfamidegroups, especially however sulfonic acid groups, as well as dyestuffs ofother classes, e. g. acid triarylmethane or anthraquinone dyestuffs.However, it is also possible to use, for. the present process, asdyestuffs which contain acid groups, most so-called substantivedyestuffs which always contain acid groups and which are usually .used.for dyeing and printing cellulose fibers, Such substantive dyestuffswith acid groups are generally disazo or polyazo dyestuffs andimaypreferably contain sulfonic acid groups as the acid groups. In View ofthe non-aqueous character of the thickenerit is normally preferable touse dyestuffs Which are soluble in the thickeners employed, or to usethe dyestuffs in a formwhich is as free as possible of inorganic solids,i. e. in concentrated form, since otherwise defects due'to insuiiic'ientsolubility may be encountered. On the other hand, the dyestuffs maycontain metals suchas copper, cobalt, nickel, iron and, especially,chromium in complex combination.

The non-aqueous thickeners used for preparation of the-printingpastes,may contain, as thickening agents, preferably water-insoluble vinylpolymers, especially polyvinyl acetate, polyvinyl chloride, as well asmixed acetate-chloride polymers, severally orin admixture with eachother. Such thickening agents are soluble or swellable in manynon-aqueous solvents or thickening agents, e. .g. in cycloh'exanone,butyl acetate, glycol monoalkyl ethers such as glycol monoethyl ether.In this connection, is advantageous to.

select solvents, e. g. hutyl acetate, which exert an appreciablesoftening action and/or to add softening agents, such asdibutyl'phthalate.

Of particular significance to the present iiivention, is the addition tothe non-aqueous thickener, of an agent which splits oii" acid whenheated. said. agent may be any of the conventional agents of this kind,e. g. of the kind whichlih acid by dissociation of asalt or by saponifiitS-on; clan ester. In selecting the agent which splits ofi acid, it isof course necessary to assure a certain compatibility with thenon-aqueous thickener. Acid-liberating agents which naturally containWater or are naturally strongly hygroscopic may give rise todifliculties, but use may be made among others of ammonium tartrate,ammonium thiocyanate, and malonic acid diethyl ester, although ammoniumchloride and ethyl tartrate are especially advantageous because of theirgood action and compatibility with the non-aqueous thickeners.

In the preparation of printing pastes, the quantity of dyestuii to beused naturally depends upon the dyeing strength which is desired torealize by the printing. The relative proportion of solvent andpolymerizate used as thickener should be so selected that a paste isproduced which can be printed with the usual printing apparatus. Indetermining the amount of acidliberating agent to be added, it is to benoted that with increasing quantities of such agent, for example betweenabout and 60 grams of ethyl tartrate per kilogram of printing paste, theimproving action is progressively increased, while with a furtherincrease, e. g. between about '70 and 80 grams per kilogram of printingpaste, a maximum is attained which is no more or at least notappreciably exceeded if the quantity of acidliberating agent is furtherincreased. When ammonium chloride is used, a quantity of grams perkilogram generally sufiices to give an optimum action, while greateramounts tend to give an undesirable gelation with many printing pastes.

The printing process, whereby textile material is printed with a pasteaccording to the invention, is per se no part of the latter and anyconventional process, such as hand printing or the like, may beemployed. The material being printed may advantageously be wool muslin,but lighter fabrics and cheviot may also be used. While the usualprinting processes are practically restricted to chlorinated wool, thepresent invention makes it possible to print unchlorinated wool also,without entailing any appreci-- able decrease in dye strength andbrilliance.

Prints obtained according to the present invention may be used afterdrying, if desired, without being subjected to any aftertreatment, ifthe product will not be exposed to conditions which require wet fastnessand fastness to rubbing. Such prints are advantageous in that they canbe rolled up, after drying, and stored for long periods of time, andthat their fastness properties are substantially improved when they aresubjected to a steaming or setting treatment such as is usual in theconventional handling.

of wool, for example in decatizing wool. It may be that theacid-liberating agent functions during such treatment to effect a fixingof the dyestuff on the fiber, bringing the normal aflinity of thedyestuif for the fiber into play. In any event, the appearance of such afixing reaction is surprising since it would be expected that-thedyestuff would be embedded in the water-insoluble thickening agent, andtherefore could not come into reaction with the fiber. In ccmparisonwith the usual printing process with aqueous pastes, printing accordingto the present invention presents the advantage that it is unnecessaryto remove the thickening agent, and in comparison with theaforementioned prior process wherein the dyestuii is fixed on the fiberby means of binding agents, the advantage-that stiffening of the printedplaces may be avoided without encountering poor fixation of thedyestuif. It is also possible, if desired, to eifect fixation of theprints according to the invention by means of a normal steamingtreatment directly following the printing. Of great importance is thefact that the otherwise necessary rinsing and washing treatment for theremoval of the thickening agent is not necessary according to thepresent invention.

This makes it possible to use the present invention in many cases wherehitherto no suitable printing process has been available. In manyinstances, the character of the material or of the area to be printedexcluded any possibility of a washing treatment for the removal of thethickening agent, for example in the case of certain taffeta fabrics forchildren or jacquard decorating material made of natural silk or Wool ormixed fabrics containing such fibers. In the case of jacquard fabric, aWashing treatment displaces the fibers, while in the case of taffeta,creases and wrinkles are produced which can hardly be removed. With manyunchlorinated wool fabrics and wool-mixed fabrics, there is also thediificulty that washing will cause unjdesired shrinking or that ayellowish coloration will develop on drying.

The following examples further illustrate the present invention, withouthowever being at all limitative thereof. In such examples, thepartsunless otherwise indicated-are parts by. weight, percentages arepercentages by weight, and temperatures are in degrees centigrade.

Example 1 A printing paste, prepared by admixing the following:

10 parts of the dyestufi,

300 parts of ethyl glycol, 250 parts of cyclohexanone, 150 parts ofdibutyl phthalate,

parts of butyl acetate,

50 parts of a solution which contains, per 100 parts, 54 parts ofacetone, 4 parts of butyl acetate, 20 parts of tricresyl phosphate, 6parts of polyvinyl acetate-chloride mixed polymer and 16 parts ofalcohol-moistened nitrocellulose, parts of polyvinyl chloride, parts ofethyl tartrate.

1000 parts is homogenized in a wet-dye mill. The paste is used forprinting on wool muslin, which is then dried and treated for ten minutesin a Mather- Platt apparatus.

Example 2 1000 parts Example 3 Chlorinated wool muslin is printed with.a printing paste of the following composition:

parts of dyestuff,

125 parts of ethyl glycol,

300 parts of cyclohexanone,

100 parts of dibutyl phthalate,

250 parts of butyl acetate,

50 parts of solution (as in preceding examples) 65 parts of polyvinylchloride,

100 parts of ethyl tartrate.

1000 parts Fixing is effected by decatizing the wool on a hot-pressingmachine.

The indicated paste may bereplaced by any one of the following pastes:

Parts by W eight- Printing Paste Dyestuff l0 l0 l0 Ethyl Glycol 125 125280 Oyclohexanonc t 300 300 300 Dibutyl Phthalate... 100 100 100 ButylAcetate .i 250 "250 130 Solution (as abovc) H i 50 50 50 PolyvinylChloride .l 65 (55 65 Ammonium Tartratc 100 Ammonium Thiocyanate 100Ammonium Chloride... 65

Total .i 1,000 1.000 1, 000

In each case, the chlorinated wool may be replaced by unchlorinated woolmuslin, light Wool cloth or cheviot.

Example 4 Chlorinated wool fabric is printed with a printing' paste ofthe following composition:

parts of dyestuff,

parts of ethyl glycol,

parts of cyclohexanone,

parts of dibutyl phthalate,

parts of butyl acetate,

parts of acetone,

parts of alcohol-moistened nitrocellulose, parts of polyvinyl chloride,

parts of ethyl tartrate.

parts The'printed fabric may be hot-pressed or steamed, whereupon theacid-eliminating agent is activated and the dyestufi is fixed.

In lieu of chlorinated wool fabric, use may also As the dyestufi in thepreceding examples, use

may be'made inter alia of any of the following.

mula

(green) g 9. Dyestufi' from diazobenzene and l-(2-chloro-5-sulfophenyl)pyrazolone 3 carboxylic acid (yellow);

10. Dyestuff from diazobenzene and 1-(2-ch1oro-5-sulfophenyl)S-methylpyrazolone (yellow);

11. Chromium compound of the dyestufi from 2-diazo-l-hydroXy-4-nitrobenzene 6 sulfonic acid and acetic acid anilide(yellow) 12. Chromium compound of the dyestuff from 2-diazo-lhydroxy-4-nitrobenzene 6 sulfonic acid andl-phenyl-l-1nethyl-pyrazolone (orange);

l3. Chromium compound of the dyestufi from2-diazo-1-hydroxybenzene-4-sulfamide and 1- (3-sulfamidophenyl)3 methylpyrazolone (orange);

14. Chromium compound of the dyestuif from 2-diazo-l-hydroxy 4chlorobenzene-G-sulfonic acid and l-pheny1-3-methylpyrazolone (orange);

15. Cobalt compound of the dyestuff from2-diazo-1-hydroXybenzene-4-sulfamide and 2-hydroxynaphthalene (red);

16. Chromium compound of the dyestufi" from 1-diazo-2-hydroxynaphthalene 4 sulfonic acid and1-phenyl-3-methyl-pyrazolone (red);

17. Dyestuff of the formula SOsH SOaH

18. Dyestuff obtained by condensation of 1 mol of cyanuric acid chloridewith 1 mol of 1-amino 4 (4-aminopheny1)aminoanthraquinone-2',3'-disulfonic acid, 1 mol of 4-amino-4'-hydroxy-Ll-azobenzene-3 carboxylic acid and 1 mol of aniline (blue) 19.Condensation product from 2 mols dehydrothio-p-toluidine-monosulfonicacid and 1 -mol of 4,4dinitrostilbene-2,2'-disulfonic acid withsubsequent oxidation with hypochlorite (yellow).

Having thus disclosed the invention, What 'is claimed is:

1. In a process for printing a textile structure of wool with a dyestuficontaining an acid group, the improvement which consists of applying thesaid dyestufi with the aid of a printing paste including a non-aqueousthickener containing a water-insoluble vinyl polymer and an acidliberating agent. I

2. In a process for printing a wool fabric with a dyestuff containing anacid group, the improvement which consists of applying the said dyestufiwith the aid of a printing paste including a nonaqueous thickenercontaining polyvinyl chloride and an acid-liberatin agent, and thensteaming the printed product.

3. A non-aqueous printing paste containing, as special assistants, aWater-insoluble vinyl polymer and an acid-liberating agent, in additionto a dyestufi having afiinity for animal fibers.

4. A non-aqueous printing paste containing an acid dyestuff and anon-aqueous thickener containing a water-insoluble vinyl polymer and anacid-liberating agent.

5. A non-aqueous printing paste containing a substantive dyestuff and anon-aqueous thickener containing a water-insoluble vinyl polymer and anacid-liberating agent.

6. A non-aqueous printing paste containing an acid dye-stuff and anon-aqueous thickener containing a water-insoluble vinyl polymer, asoftening agent and an acid-liberating agent.

7. A non-aqueous printing paste containing a substantive dyestuff and anon-aqueous thickener containing a water-insoluble vinyl polymer, asoftening agent and an acid-liberating agent.

8. A non-aqueous printing paste containing an acid dyestufi and anon-aqueous thickener containing polyvinyl chloride and ethyl tartrateas acid-liberating compound.

9. A non-aqueous printing paste containing an acid dyestuff and anon-aqueou thickener containing polyvinyl chloride and ammonium chlorideas acid-liberating compound.

' ERWIN MEIER.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS

1. IN A PROCESS FOR PRINTING A TEXTILE STRUCTURE OF WOOL WITH A DYESTUFFCONTAINING AN ACID GROUP, THE IMPROVEMENT WHICH CONSISTS OF APPLYING THESAID DYESTUFF WITH THE AID OF A PRINTING PASTE INCLUDING A NON-AQUEOUSTHICKENER CONTAINING A WATER-INSOLUBLE VINYL POLYMER AND AN ACIDLIBERATING AGENT.